The eighth seed - who was on an 11-match winning run on the red dust in Paris - lost in straight sets, 6-4, 6-4, to Greek 17th seed Maria Sakkari on Court Philippe Chatrier on Wednesday.
Sakkari’s victory seals an unexpected women’s semi-final lineup, with the world no18 set to face Barbora Krejcikova for a place in Saturday’s showpiece after the Czech came back to defeat American teenager Coco Gauff 7-6, 6-3.
In Thursday’s other semi-final, Anastasia Pavlyuchenkova - who beat the likes of third seed Aryna Sabalenka and Victoria Azarenka en route to the last eight before an epic win over Elena Rybakina - will battle unseeded Slovenian Tamara Zidansek, who also won a quater-final thriller against Paula Badosa.
Of that semi-final quartet, only Pavlyuchenkova has previously been beyond the fourth round at a Grand Slam, though Krejcikova is a two-time doubles champion.
"Everybody, they just put a label on me like, 'Yeah, you play doubles. You are a doubles specialist.' But I never thought I just want to be a doubles specialist," she said after beating Gauff.
"So I was just working hard all the time. I just wanted to play singles. It was really, like, frustrating that I just wasn't able to get there. But I always felt ... sooner or later, I'm just going to get there."